JPH03293669A - Photosensitive lithographic printing plate that does not require dampening water - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a negative type photosensitive lithographic printing plate that does not require dampening water.

(Prior Art) Many negative type photosensitive lithographic printing plates that do not require dampening water have been proposed, in which the photosensitive layer is made of a quinone diazide compound and the ink repellent layer is made of silicone rubber. For example, JP-A-55-594
It is described in Japanese Patent Application Laid-Open No. 110249/1986, etc.

However, all of these photosensitive lithographic printing plates that do not require dampening water require a developer or a pre-development treatment solution containing an organic solvent. Treatment liquids based on organic solvents are not very desirable in terms of the Fire Service Act, and are also not desirable in terms of labor and environmental hygiene. It is also impossible to use the processing liquid together with a lithographic printing plate that uses dampening water. For these reasons, there is a desire for a photosensitive lithographic printing plate that does not require dampening water and can be developed mainly with an alkaline aqueous solution or with an alkaline aqueous solution.

Furthermore, conventional negative-working photosensitive lithographic printing plates that do not require dampening water using quinonediazide compounds suffer from light fog when handled under white fluorescent light, and the silicone rubber layer in the non-image areas is exposed when the next development process is carried out. The underlying photosensitive layer erodes, damaging the silicone rubber layer and impairing ink repulsion. Therefore, there is a need for a negative-working photosensitive lithographic printing plate that does not require dampening water and has a photosensitive layer with improved resistance to light fog (hereinafter referred to as "safelight property").

(Object of the Invention) It is an object of the present invention to improve the above-mentioned problems and provide a negative-working photosensitive lithographic printing plate that does not require dampening water and can be developed with a developer mainly containing an alkaline aqueous solution or an alkaline aqueous solution and has excellent safelight properties. .

(Means for Solving the Problem) As a result of extensive research, the present inventors have found that the photosensitive layer contains at least (A) a 1,2-naphthoquinone-2-diazide-4 sulfonic acid ester compound and (B) a phenolic compound. The above object was achieved by having a polymer having a structural unit having a hydroxyl group in its molecular structure.

The present invention will be explained in detail below.

As the substrate used in the present invention, any substrate can be used as long as it has the flexibility to be set in a normal lithographic printing machine and can withstand the load applied during printing, and there are no particular restrictions on the substrate including the layer structure. . Examples include papers such as coated paper, metal plates such as aluminum plates, and plastic films such as polyethylene terephthalate.

The substrate used in the present invention is preferably an aluminum plate or a composite material of aluminum foil and other materials, and from the viewpoint of rigidity, an aluminum plate is particularly preferable.

As the primer layer used in the present invention, any of various known primer layers can be applied, but for example, those made by heating and curing epoxy resin, polyurethane resin, etc. using an appropriate curing agent, etc. The primer layer described in JP-A No. 60-229031, such as the primer layer described in JP-A-60-229031, such as the one obtained by photocuring a layer made of a photoduplex type curable resin, etc., can be used. Furthermore, a primer layer obtained by photocuring a layer mainly composed of a diazo resin and a hydroxyl group-containing polymer is also preferably used. Such diazo resins are used, for example, in Photographic Science and Engineering (Photo, Sci).
, Eng.) Volume 17, Page 33 (1973), U.S. Pat. -7
Diazo compounds and active carbonyl compounds (for example, formaldehyde, acetaldehyde, benzaldehyde, etc.) whose production methods are described in Publication No. 8340, etc.
A diazo resin obtained by condensing the above in an acidic medium such as sulfuric acid, phosphoric acid, or hydrochloric acid, and a diazo compound whose manufacturing method is described in Japanese Patent Publication No. 49-4001, and a diphenyl ether derivative are subjected to a condensation reaction. A diazo resin obtained by the above method can be used. Particularly preferred is a condensate of paradiazodiphenylamine and formalin.

The counter anion of the diazo resin used in the present invention is
It contains an anion that forms a stable salt with the diazo resin and makes the resin soluble in organic solvents.

These include organic carboxylic acids such as decanoic acid and benzoic acid;
Contains organic phosphoric acids and sulfonic acids such as phenyl phosphoric acid,
Typical examples include methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid and anthraquinonesulfonic acid, 2-hydroxy-4-methoxyhensiphenone-5-sulfonic acid. , hydroquinone sulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl-5
Aliphatic and aromatic sulfonic acids such as sulfonesophthalate 2.2',4.4'-tetrahydroxybenzophenone, 1,2.3-trihydroxybenzophenone, 2
．． Aromatic compounds containing hydroxyl groups such as 2',4-trihydroxyhensiphenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, CfO, IO4
Examples include perhalogen acids such as . Among these, halogenated Lewis acids and hexafluorophosphoric acid are preferred, and hexafluorophosphoric acid is particularly preferred. The weight average molecular weight of the coupled product with β-naphthol measured by gel permeation chromatography (CPC) is 200 to 100.
00 (in terms of styrene) is preferable, and the range is 500 to 5
A range of 000 is more preferred.

In the present invention, the proportion of the diazo resin in the primer layer is usually 1 to 90% by weight, preferably 3 to 60% by weight.

In addition, as a hydroxyl-containing polymer used with diazo resin, alcoholic hydroxyl group-containing poly(meth)acrylic acid (hereinafter, both acrylic and methacrylic are collectively referred to as (meth)acrylic... ... is written.

) are preferably used.

Examples of monomers having alcoholic hydroxyl groups include 2-hydroxyethyl (meth)acrylate, N-(4
-hydroxyethylphenyl) (meth)acrylamide, hydroxy-methyldiacetone (meth)acrylamide, and the like. Especially 2-hydroxyethyl (meth)
Acrylates are preferred.

Examples of heptamers copolymerizable with the above-mentioned hydroxyl group-containing heptamers include (1) heptamers having an aromatic hydroxyl group, such as N-(4
-Hydroxyphenyl)(meth)acrylamide, o-
, m-, p-hydroxystyrene, o-, m-, p-hydroxyphenyl-(meth)acrylate (2) α, β of (meth)acrylic acid, maleic anhydride, etc.
-Unsaturated carboxylic acid, (3) methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate , cyclohexyl (meth)acrylate,
(meth)octyl acrylate, (meth)acrylic acid-2
- (Substituted) alkyl (meth)acrylates such as chloroethyl, 2-hydroxyethyl (meth)azilylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, N-dimethylaminoethyl (meth)acrylate, (4 )(meth)acrylamide, N-totyrol(meth)acrylamide, N-ethyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, phenyl(meth)acrylamide ) acrylamide, N-nitrophenyl (meth)acrylamide, N
-ethyl-N-phenyl (meth)acrylamide etc. (
(meth)acrylamides, (5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (6) vinyl acetate, vinyl chloroacetate, vinyl butyrate , vinyl esters such as vinyl benzoate, (7) styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, (8) methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, etc. (9) olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, (10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, (meth)acrylonitrile, etc. Particularly preferred are the above groups (1) to (3). The amount of hydroxyl group-containing monomer in the hydroxyl group-containing polymer is not particularly limited, but preferably 5 to 100
% by weight, particularly preferably from 20 to 100% by weight.

The weight average molecular weight of the hydroxyl group-containing polymer of the present invention measured by GPC method is 5,000 to 1,000,000 (in terms of styrene)
is preferred. If the value is lower than 5,000, it may be damaged by the coating solvent or developer of the photosensitive layer even after photocuring, and 10
If the value is larger than 00000, it is difficult to select a coating solvent.

The proportion of the hydroxyl group-containing polymer in the primer layer is usually 10 to 99% by weight, preferably 40 to 97% by weight.

In the present invention, the primer layer contains, in addition to the above-mentioned components, fillers such as titanium oxide and zinc oxide, or antihalation agents, coloring agents such as dyes and pigments, coating properties improvers, plasticizers, stabilizers, etc. It may also contain agents, oil-sensitizing agents, etc. in an amount not exceeding 50% by weight.

As the above-mentioned dye and coatability improving agent, the same ones as those contained in the above-mentioned photosensitive layer are used.

Examples of plasticizers for imparting flexibility and abrasion resistance to coating films include butylphthalyl, polyethylene glycol,
Examples include tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrafurfuryl oleate, oligomers of acrylic acid or methacrylic acid, etc. .

In addition, in order to improve the printing ink adhesion of images, various additives having hydrophobic groups, such as p-octylphenol/formalin novolak resin, Pt-butylphenol/formalin novolak resin, p-t-butylphenol/benzaldehyde resin, rosin, etc. Modified novolak resins such as modified novolak resins can also be used by adding 0-naphthoquinonediazide sulfonic acid esters (esterification rate of OH group: 20 to 70 mol %) of these modified novolak resins.

The above-mentioned photocurable diazo resin or a composition containing the same and a hydroxyl group-containing polymer are dissolved in an appropriate organic solvent together with other additives added as necessary, and then applied onto a support and dried. After that, it is exposed to light to completely decompose the diazo resin and harden it, thereby forming a primer layer.

Primer layer thickness is IIIg/dI112-200
It is preferably 112 mg/dI, more preferably 3 mg/dm2 to 100 mg/dm''.

(Photosensitive layer) In the present invention, various known compounds can be used as the 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester compound (hereinafter simply referred to as "diazide compound") contained in the photosensitive layer. However, ester compounds of 1,2-naphthoquinone-2-diazide-4-sulfonic acid and polycondensation resins of phenols and aldehydes or ketones are particularly preferably used.

Examples of the phenols include phenol, 0-
Cresol, m-cresol, p-cresol, 3,5
- Monohydric phenols such as xylenol, carvacrol, and thymol, dihydric phenols such as catechol, resorcinol, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these are formaldehyde and benzaldehyde. Further, examples of the ketone include acetone, methyl ethyl ketone, and the like.

Specific examples of the polycondensation resin include phenol/formaldehyde resin, m-cresol/formaldehyde resin, P-cresol/formaldehyde resin, and m-cresol/formaldehyde resin.
, p-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, pyrogallol/acetone resin, and the like.

1 for the OH group of the phenol of the diazide compound
, the condensation rate (reaction rate for one OH group) of 2-naphthoquinone-2-diazide-4-sulfonic acid is 15 to 80%.
is preferable, and more preferably 20 to 60%.

Furthermore, as a diazide compound, polyhydroxy compound 1
．． Examples of such compounds include 2-naphthoquinone-2-diazide-4-sulfonic acid ester compounds;
For example, 1,2-naphthoquinonediazide-4-sulfonic acid cyclohexyl ester, l(1,2-naphthoquinonediazide-4-sulfonyl)-3,5-dimethylpyrazole, 1,2-naphthoquinonediazide-4-sulfonic acid-
4''-hydroxydiphenyl-4#-azo-β-naphthol ester, 2'-(1,2-naphthoquinonediazide-4-sulfonyloxy)-1=hydroxy-anthraquinone, 1.2naphthoquinonediazide-4-sulfonic acid- 2,4-dihydroxybenzophenone ester, 1,
2-naphthoquinonediazide-4-sulfonic acid-2,3,
4-trihydroxybenzophenone ester, 1,2 naphthoquinonediazide-4-sulfonic acid-2,3°4'
4'-tetrahydroxybenzophenone ester, 1
．． Condensate of 2 moles of 2-naphthoquinonediazide-4-sulfonic acid chloride and 1 mole of 4,4'-dihydroxy-1,1'-diphenylsulfone, 1 mole of 1,2-naphthoquinonediazide-4-sulfonic acid chloride and Puru 10597
Examples include 1 mol of condensate.

Furthermore, polyurethane resins such as 1 and 2 as shown below can be used.
-Naphthoquinone-2-diazide-4-sulfonic acid ester compounds may also be used.

C.N.

(however, n is 2 to 30 Represents an integer of 0.

) Furthermore, as the diazide compound, an ester compound of a vinyl polymer having a phenolic hydroxyl group and 1,2-naphthoquinone-2-diazide-4-sulfonic acid can also be used. The vinyl polymer having a phenolic hydroxyl group that forms such an ester compound is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and preferably the structural unit having a phenolic hydroxyl group described below is incorporated into the molecular structure. The same vinyl polymer as that contained therein is used.

As the compound of the present invention, each of the above compounds may be used alone or in combination of two or more. The proportion of the compound of the present invention in the photosensitive composition of the present invention is preferably 5 to 60% by weight, particularly preferably 10 to 60% by weight.
It is 50% by weight.

Next, in the present invention, the polymer (B) having a structural unit having a phenolic hydroxyl group in its molecular structure, which is contained in the photosensitive layer together with the diazide compound, preferably has the following formula (
Examples include polymers containing at least one structural unit of a) to [d].

CON R, -(-Ate1 -OH OO -〇A-)-i -0H B-○H H In the formula, R4 and R3 each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. be. R6 represents a hydrogen atom, a halogen atom, or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R7 represents a hydrogen atom, an alkyl group, an alkyl group, or an aralkyl group, preferably an allyl group. A represents an alkylene group which may have a substituent and which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of O to 10, and B may have a substituent. Represents a phenylene group or a naphthylene group which may have a substituent.

The polymer (B) used in the present invention preferably has a copolymer type structure, and the above-mentioned formula (a)
Examples of monomer units that can be used in combination with the structural units represented by (d) are ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; styrene, α-methylstyrene, p - Styrenes such as methylstyrene and p-chlorostyrene; Acrylic acids such as (meth)acrylic acid; Unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride; Methyl (meth)acrylate, (meth) ) Ethyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, dodecyl (meth)acrylate, 2-chloroethyl (meth)acrylate, phenyl (meth)acrylate, methyl α-chloroacrylate , esters of α-methylene aliphatic monocarboxylic acids such as ethyl ethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl (meth)acrylate, N-
Nitriles such as esters or amides of (meth)acrylic acid containing an alcoholic hydroxyl group such as (4-hydroxyethylphenyl) (meth)acrylamide, hydroxy-methyldiacetone (meth)acrylamide, etc. (meth)acrylate; ) Amides such as acrylamide;
Anilides such as (meth)acrylamide, p-chloro(meth)acrylanilide, m-nitro(meth)acrylanilide, m-methoxy(meth)acrylanilide; vinyl acetate, vinyl propionate, vinyl benzoate , vinyl esters such as vinyl butyrate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether; vinyl chloride; vinylidene chloride: vinylidene cyanide; 1-methyl-1-methoxyethylene, 1
．． Ethylene derivatives such as 1-dimethoxyethylene, 1.2-dimethoxyethylene, 1.1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene; N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N -N-vinyl compounds such as vinylpyrrolone and N-vinylpyrrolidone; and other vinyl monomers. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

These monomers are blocks in the polymers of this invention.

Typical specific examples of the polymer (B) used in the present invention, which may be bonded in either a grafted or random state, are listed below. In addition, in the compounds shown below, s, 12. m and n are simply the mole percent of the structural unit, respectively.
It does not mean that each constituent unit exists collectively. ) Exemplary compound (a) CH.

II CH3 (Mw=3 00° Mw/Mn=2.5.

m:n:ji! =30:40:30) (b) CHl CH3 *(CH2-CCHz CH)-k COOCR.

COOCC00 C2H5( 00° Mw/Mn=2.1.

m:n:l:ni=30:30:36.5:3.5
) (C) (MW=2 00°Mw/Mn=6.9°m:n:/=30:40:30) (d) m:n:j! = 20:35:45) (e) O (Mw = 33 00°Mw/M n = 7.

m:n:f=38:60:2) (f) CH3 CHl (Mw=40000゜ Mw/Mn=3.5.

m:n:f=20:60:20) (g) CH3 CH3 CH.

CH.

*ICl2 CI division---HCHz-Cji]-N OOH (Mw=35000゜ Mw/Mn=7.9.

m:n:f:ni:5=20:15: 30:33:2) (h) CH.

(Mw=35 00 Mw/Mn=3.5 m:n:f=30:30:4
0)(i) H1ll CH3H (Mw=5 000°Mw/Mn -8,2.

m:n:f=20:40:40) (Mw=20000゜ MW/Mn=3.5.

manmi1:1) 0■ (Mw=51000.Mw/Mn=5.7゜m:n:=
1:1) (1) CH3H (Mw=35000.Mw/Mn=3.8゜m: n
: t2=30 : 35 : 35) As the vinyl polymer used in the present invention, the above-mentioned polymers may be used alone or in combination of two or more. Also,
It can also be used in combination with other polymer compounds.

In the present invention, a novolak resin may be used as a binder in an amount of 0.1 to 60% (weight ratio) based on the polymer (B).

Such novolac resins include, for example, phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensate resin as described in JP-A-55-57841, and JP-A-55-1275. Examples include copolycondensate resins of p-substituted phenol and phenol or cresol and formaldehyde, as described in Japanese Patent No. 3.

The molecular weight of the novolac resin is preferably a number average molecular weight (hereinafter abbreviated as “Mn”) of 3×10” to 7.50×
lO3, weight average molecular weight (hereinafter abbreviated as "MW") is l
Xl0"~x3x104, more preferably Mn is 5x1
02 to 4 x 10, and Mw is 3 x 10" to 2 x 10'. The molecular weight of the present invention was measured by the method described in Synthesis Example 1 in Examples below for both Mn and Mw.

In the present invention, the polymer (B) is used as a binder, and is used in the photoreceptor composition in an amount of 5 to 95% by weight, preferably 20 to 90% by weight.

A photosensitive layer is obtained from the above components, and in addition, an exposure visible image imparting agent and a dye are generally added.

As the exposure visible image imparting agent, a compound that generates an acid upon exposure is generally used, and as the dye, a compound that forms a salt with this acid is generally used.

Compounds that generate acid upon exposure to light include
or a trihaloalkyl compound or a diazonium salt compound represented by V is preferably used.

(Xa is a trihaloalkyl group having 1 to 3 carbon atoms, W
is N, S, Se or P, Z is O, N, S, Se or P, Y is a group having a chromophore group and consisting of nonmetallic atoms necessary to cyclize W and Z. ) Ar Nx (Formula %) Specific exemplary compounds include - formula (1) oxadiazole compounds having a benzofuran ring such as U;
2-trichloromethyl-5-(p-methoxystyryl)-1, which is described in JP-A-54-74728,
Examples include 3,4-oxadiazole compounds.

In addition, as compounds of -formulas ■ and ■, JP-A-53-3
4(2,4-dimethoxy-4-styryl)-6-)lichloromethyl-2-pyrone compound described in Publication No. 6223 1; 2. 4-bis-(trichloromethyl)-
6-p-methoxystyryl-3-) riazine compound, 2
, 4-bis(trichloromethyl)-6-p-dimethylaminostyryl-3-) riazine compounds, and the like.

The diazonium salt compound is preferably a diazonium salt that generates a strong Lewis acid upon exposure to light, and a counter ion of an inorganic compound is recommended as the counter ion portion.

Specific examples include aromatic diazonium salts in which the anion moiety of the diazonium salt is at least one of phosphorus fluoride ion, arsenic fluoride ion, antimony fluoride ion, antimony chloride ion, tin chloride ion, bismuth chloride ion, and zinc chloride ion. Paradiazophenylamine salt is preferred.

The amount of the exposure visible image imparting agent contained in the total photosensitive layer is preferably 0.01 to 20% by weight, more preferably 0.1 to 20% by weight.
20% by weight, especially 0.2-10% by weight.

On the other hand, as the dye, any compound that forms a salt with a generally known acid can be used, such as triphenylmethane dyes, cyanine dyes, diazo dyes,
Examples include styryl dyes. Specifically, Victoria Pure Blue 80, Ethyl Violet, Crystal Violet, Brilliant Green, Pesic Tsuksin, Eosin, Phenolphthalein, Xylenol Blue Congo Red, Malachite Green, Oil Blue, +603, Oil Pink +312, Cresol Red, Examples include auramine, 4-p diethylaminophenylimino naphthoquinone, leucomalachite green, leuco crystal high olent orange (■), and the like. The amount of the dye added is preferably about 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, based on the total photosensitive layer.

The above-mentioned photosensitive composition is a paint dissolved in various solvents, such as cellosolves such as methyl (ethyl) cellosolve and methyl (ethyl) cellosolve acetate, coating solvents such as dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, and trichloroethylene. A photosensitive layer is obtained by coating the above-mentioned brimer using a known method and drying it. The thickness of the photosensitive layer is 0.5
It is preferably 1 mg/dm2 to 50 mg/dm2, more preferably 1 mg/dm2 to 50 mg/dm.

(Silicone Rubber Layer) The silicone rubber layer used in the present invention is preferably a somewhat crosslinked organopolysiloxane. The organopolysiloxane usually has a molecular weight of 100,000 to several hundred thousand.

The organopolysiloxanes are classified into condensed type and addition type depending on the method of crosslinking.

In the condensed type, crosslinking is performed by a condensation reaction, and water, alcohol, organic acid, etc. are released by the reaction. Particularly useful condensation type silicone rubbers include those obtained by reacting a mixture of a linear organopolysiloxane having hydroxyl groups at both ends or a part of the main chain with a silicone crosslinking agent, and reacting the hydroxyl groups with the silicone crosslinking agent. In either case, adding a condensation solvent is advantageous in terms of crosslinking speed.

The organopolysiloxane has the following repeating units in its main chain.

1 ← 5i-0-)- 2 In the formula, R1 and R2 are alkyl, aryl, alkenyl, or a combination thereof, each of which may have a substituent such as a cyano group, a halogen atom, or a hydroxyl group, and a methyl group,
A phenyl group, a vinyl group, and a trifluoropropyl group are preferred, and a methyl group is particularly preferred.

The above-mentioned silicone crosslinking agents include the so-called acetic acid-removal type, oxime-elimination type, alcohol-elimination type, deamination type, dehydration type, and those having a functional group represented by -OH (in the formula, R and R' are alkyl groups). Examples include condensed silicone crosslinking agents such as molds. Examples of such crosslinking agents include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane,
Diethyldiacetoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, methyltris(acetoneoxime)silane, methyltri(N-methyl, N
-acetylamino)silane, vinyltri(methylethylketoxime)silane, methyltri(methylethylketoxime)silane, or oligomers thereof.

All of these crosslinking agents are organopolysiloxane 10
The amount is preferably in the range of 0.5 to 30 parts by weight relative to 0 parts by weight. Particularly preferably 1 to 20 parts by weight.

Examples of the condensation catalyst include organic carboxylic acids, titanate esters, naphthenic acids, and the like.

The addition type refers to an unsaturated group in the main body, such as a vinyl group (-C
H=CH2) is crosslinked by the addition of hydrogen in the crosslinking agent.

Specifically, examples include vinyl group-containing organopolysiloxanes, hydrogenated organopolysiloxanes, and the like mixed with platinum-based catalysts (for example, chloroplatinic acid).

The organopolysiloxane has repeating units similar to those of the condensed type in the main chain.

In the silicone rubber layer of the present invention, either or both of condensation type silicone rubber and addition type silicone rubber can be used.

Furthermore, it is also possible to use a condensation-addition type organopolysiloxane having a hydroxyl group, an unsaturated group, etc. in one organopolysiloxane.

Among the commercial products available as the silicone rubber according to the present invention, preferred examples include KS-705F and K manufactured by Shin-Etsu.
E-41, 42, 44, Toshiba Silicone (manufactured) YE55
05, YF3802, Higashi Rejirin (manufactured) SH-781
, PRX-305, 5H-237 and other condensation silicone rubbers, and Shin-Etsu KS-837, KE-103, KE-
106, KE-1300, Toshiba'i Ricoh 7 (manufactured) TS
E3032, RTU-B, Toshi Silicone (manufactured by) SI (
Examples include addition-type silicone rubber such as -9555.

Further, for the purpose of improving the strength of silicone rubber, an inorganic filler such as silica, titanium oxide, or aluminum oxide may be added, and silica is particularly preferably used.

From the viewpoint of dispersibility or dispersion stability, such fillers preferably have an average particle diameter of 500 μm or less.

Furthermore, in addition to the above-mentioned components, a reactive silane compound having an isocyanurate group may be added to the silicone rubber layer used in the present invention in order to improve the adhesion to the photosensitive layer.

The reactive silane compound having an isocyanate group used in the present invention is represented by the following formula.

R8 to 0/＼ri0 1 Particularly preferred are those represented by the following formula.

C3H6Si (OMe) 3 0\／N\riO C.C. 1 The amount of the reactive silane compound added is: organo 0.5% to 1 for polysiloxane 0%, preferably is 1-5%.

In the present invention, the thickness of the silicone rubber layer is preferably as thin as possible from the point of view of image quality and developability, and on the other hand, a certain degree of thickness is required from the point of view of rigidity resistance, printing stains, etc., so it is generally 3 mg/dm. "~50 mg/di2 is preferred, 5 mg/dm" ~30 mg/di"
is more preferable.

(Protective layer) Furthermore, in the photosensitive lithographic printing plate that does not require dampening water of the present invention, a protective layer may be provided on the silicone rubber layer, and as a method for providing a nuclear protective layer, a polypropylene film described in Japanese Patent Publication No. 61-614 may be used. How to laminate etc. and JP-A-61-27
A method of coating a high molecular weight polymer described in No. 545 is known.

(Exposure and development treatment) The photosensitive lithographic printing plate that does not require dampening water, obtained as described above, can be used in the following methods.

A printing plate can be obtained by closely adhering the lith film of the original image onto the protective layer of a photosensitive lithographic printing plate that does not require dampening water, exposing it to ultra-high pressure mercury lamps, metal halide lamps, etc., peeling off the protective layer, and developing it. .

The developer used during development is mainly an alkaline aqueous solution or an alkaline aqueous solution. Alkaline agents that can be preferably used include potassium silicate, lithium silicate,
Examples include sodium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic potassium phosphate, dibasic potassium phosphate, sodium carbonate, potassium carbonate, and the like. Among these, a developer containing an alkali silicate such as potassium silicate, lithium silicate, or sodium silicate is most preferable because it has good development gradation, and the composition of the alkali silicate is [SiO□]/ (M]-0.5 to 1.5 (here, [Si○2], (M3 indicates the molar concentration of 5 in2 and the molar concentration of the total alkali metal), and Si
A developer containing 0.8 to 8% by weight of O□ is preferably used.

Of this alkali silicate composition, especially in terms of molar ratio (S i
02:l/CM) -0.5 to 0.75 and a Sing of 0.8 to 4% by weight, because it is a developer with a low concentration and it is easy to neutralize the developer waste solution. On the other hand, a developer having a molar ratio of more than 0.75 and up to 1.3 and containing 1 to 8% by weight of SiO□ is preferably used because it has a high buffering power and a high throughput.

Furthermore, water-soluble sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite can also be added to the developer.

Further, in the developer, anionic surfactants and amphoteric surfactants such as those described in JP-A-50-51324, and JP-A-59-75255 and JP-A-60
By containing at least one of the nonionic surfactants as described in JP-A-111246, or JP-A-55-9546, JP-A-56-14.
A polymer electrolyte can also be included as described in Japanese Patent No. 2528. The amount of such surfactant added is not particularly limited, but is preferably 0.003 to 3% by weight, especially O
, OO 6-1% by weight is preferred.

Further, it is preferable that the alkali silicate contains at least 20 mol% of potassium as the alkali metal in all the alkali metals, since the generation of insoluble matter in the developer is small, and more preferably 90 mol% or more of potassium. , most preferably when the potassium content is 100 mol %.

Furthermore, the developer used in the present invention can contain an antifoaming agent. Suitable antifoaming agents include organosilane compounds.

Further, depending on the case, 10% by weight or less of a polar solvent as described below may be contained.

Gokuyoshi 1 Roasted Alcohols (methanol, ethanol, water, etc.) Enals (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl calpitol, ethyl calpitol, butyl calpitol, dioxane, etc.) Ketones (acetone, methyl ethyl ketone, etc.) Esters (Ethyl acetate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.) After development, a primer layer is applied to the image areas (ink-bearing areas), and a silicone rubber layer is applied to the non-image areas (ink repellent areas). become covered. After development, the primer layer, which is the image area, is preferably dyed for convenience in plate inspection, etc. Dyes suitably used for this dyeing include crystal violet, Victoria Pure Blue (BOH
), malachite green, etc. These dyes can be dissolved in water or a mixture of water and a solvent such as alcohol, and this solution can be used for dyeing.

(Example) Hereinafter, the dampening water-free photosensitive lithographic printing plate of the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

(Synthesis of diazide compound) Synthesis Example 1 (QD-1) 50 g of pyrogallol and 500 g of acetone were placed in a three-headed kolben set in a water lotus. After nitrogen gas was blown into the tank and nitrogen was replaced, 5 g of phosphorous oxychloride was added. The reaction temperature was kept at 20°C and the reaction was allowed to proceed for a day and night, and then the mixture was gradually poured into 15 cm of water with strong stirring to precipitate the formed polycondensate.

The precipitated resin was collected by filtration and washed with water until the pH became approximately neutral (7), and the filtered material was dried at 40'C or lower. In this way, 48 g of light brown resin was obtained.

The molecular weight of this resin was determined by GPC (Hitachi model 635, column Shodex) A804, A303, A3.
02 in series] using polystyrene as a standard. Calculation of Mn and Mw is by Tsuge et al., Journal of the Chemical Society of Japan, 197.
The measurement was carried out in accordance with the method described in 2004 (April issue), page 800, by leveling the peaks of the oligomer region (connecting the centers of the peaks and valleys). As a result, Mn is 1.20x10
3Mw was 2.12X10'.

Next, 60 g of this resin was dissolved in dioxane 720/11i2, 70 g of 1,2-naphthoquinonediazide-4-sulfonyl chloride was added, and after dissolving, 70 g of potassium carbonate aqueous solution (13% by weight) was added dropwise to the 40-50° Approximately 1 in C
After the time-spacing cotton mixing reaction, the reaction solution was poured into a large amount of diluted hydrochloric acid (13 in concentrated hydrochloric acid, 3 in in water), and the precipitated resin was collected by filtration and dried. 1.
2-naphthoquinonediazide-4-sulfonic acid ester 5
6g yellow powder resin was obtained. As a result of analysis, the condensation rate of OH groups was 30%. When the molecular weight of the ester was measured in the same way as polyhydroxy resin, Mn was 1.50X.
103, Mw was 2.32×103.

Synthesis Example 2 (QD-2) 200 g of p-cresol, 50 g of a 37% aqueous formaldehyde solution, and 2.5 g of oxalic acid were placed in a three-headed colben set in an oil path and heated while stirring. 9
It foamed violently at around 0°C, and after being temporarily cooled, the temperature was raised again to bring the internal temperature to 105°C.

After reacting for about 3 hours, the temperature was further raised to 175°C, and water was distilled off.

After 2 hours, the temperature was raised to 200°C, and the pressure was reduced to 100 mm) to distill off the residual supernatant. After 10 minutes, the reaction was stopped, and the reaction product was poured into a Teflon vat and solidified. As a result of measuring the molecular weight of this resin, Mn is 500 and Mw is 800.
Met.

Next, 60 g of this resin was dissolved in 720 d of dioxane,
70 g of 1.2-naphthoquinonediazide-4-sulfonyl chloride was added, and the same procedure as in Synthesis Example 1 was repeated to obtain 62 g of yellow powder resin of esterified product (QD-2). As a result of the analysis, the condensation rate of OH groups was 50% and the molecular weight was Mn.
=700Mw=1010.

Comparative Synthesis Example-1 (QI)-3) 50 g of pyrogallol and 350 g of acetone were placed in a three-headed colben set in a water path, and nitrogen gas was blown in to perform nitrogen substitution, and then 5 g of phosphorus oxychloride was added for polycondensation. The reaction was carried out. The reaction temperature was kept at 20°C and the reaction was allowed to proceed for a day and night, and then the mixture was gradually poured into 152 ml of water with strong stirring to precipitate the formed polycondensate.

The precipitated resin is collected by filtration and washed with water until the pH becomes approximately neutral (7). The filtered material is dried at 40°C or less. In this way, 50 g of light brown resin was obtained. Mn was 2.0OX10' and Mw was 3.40x103.

Next, 60 g of this resin was dissolved in 720 d of dioxane,
1. Add 70 g of 2-naphthoquinonediazide-5-sulfonyl chloride and dissolve, then add potassium carbonate aqueous solution (
After dropping 60 g of 13% by weight) and carrying out an open-cotton combination reaction at 40 to 50°C for about 1 hour, the reaction solution was poured into a large amount of diluted hydrochloric acid (
The precipitated resin was collected by filtration and dried. 1.2- of pyrogallol acetone resin
Naphthoquinonediazide-5-sulfonic acid ester 56g
A yellow powder resin was obtained. As a result of analysis, the condensation rate of OH groups was 20%. When the molecular weight of the ester was measured in the same way as polyhydroxy resin, Mn was 2.30X1
0”, Mw was 3.03×103.

[Synthesis of polymer (B)]

Synthesis Example 3 (Binder 1) 400 g of P-hydroxyaniline, 4 g of hydroquinone monomethyl ether, 41 acetone, and 36 pyridine
0 g was mixed and cooled from the outside using a cryogen, and when the internal temperature had dropped to -10"C, 420 g of metal acrylic acid chloride was added dropwise with stirring. The dropping temperature was adjusted so that the reaction temperature was below 0 °C. After dropping, heat at 0 to 3°C for about 2 hours.
After stirring for 1 hour and then stirring at 25°C for 2 hours, the reaction solution was concentrated to about 1/3 and mixed with dilute hydrochloric acid (pH about 1.
The resulting precipitate was suction-filtered to obtain a white solid. This white solid was dissolved in Metalnol 21 while heating, and a 5% aqueous sodium carbonate solution 21 was further added, followed by stirring at 40°C for 30 minutes. Next, this dark red solution was mixed with 5% hydrochloric acid aqueous solution 8! A large amount of precipitate was formed, which was filtered and dried to obtain a pale pink solid. This was recrystallized from a mixed solvent of ethanol and water with a melting point of 15
450 g of colorless needle-like crystals of P-hydroxymethacrylanilide having a carbon content of 5 to 156"C were obtained.

The obtained p-hydroxymethacrylanilide (HyP
MA) 53.2g, acrylonitrile (AN) 15.9
g, methyl metaallylate (MMA) 36.5 g, 2
・Hydroxyethyl methacrylate (HEMA) 3.5
g and α・α′-azobisisobutyronitrile 0.8
2 g of acetone:ethanol (1:2) mixed solvent 1
A polymer solution was obtained by dissolving in 90d and heating at 65°C after purging with nitrogen gas. Add this polymer solution to 3
The resulting white precipitate was filtered and dried to obtain 70 g of a white polymer. When the molecular weight was measured, the Mw was 4.6×10'.

Synthesis Example 4 [Binder 2] 40.0 g of p-hydroxystyrene, 20.0 g of acrylonitrile, 40 g of styrene and 1 g of α・α′-
Azobisisobutyronitrile to acetone:ethanol (
A polymer solution was obtained by dissolving in 600 d of a mixed solvent (1:1), purging with nitrogen gas, and heating at 68°C for 10 hours. This is water 5I! .

The white precipitate formed was filtered and dried to obtain 70g of polymer.
I got it. The Mw of this polymer was 47,000.

Synthesis Example 5 [Binder 3] 9 og of m-cresol, 56 g of p-cresol, 54 g of phenol, 85 g of 37% formaldehyde aqueous solution, and 2.5 g of oxalic acid were put into a three-head colchen set in an oil bath and heated while stirring. did. It foams violently at around 90"C, cools down temporarily, and then rises again to bring the internal temperature to 1.
The temperature was set to 05°C.

After reacting for about 3 hours, the temperature was further raised to 175°C, and water was distilled off.

After 2 hours, the temperature was raised to 200°C, and the pressure was reduced to 100 mmHg to distill off residual monomers. After 10 minutes, the reaction was stopped and the reaction product was poured into a Teflon hat and solidified. As a result of measuring the molecular weight of this resin, Mn was 1350 and Mw was 540.
It was 0.

[Preparation of substrate and primer layer]

Production of aluminum layer An aluminum plate with a thickness of 0.24 mm was immersed in a 3% aqueous sodium hydroxide solution to degrease it, washed with water, and then anodized in a 32% aqueous sulfuric acid solution at a temperature of 30°C and 15A/d1 for 10 seconds. After further washing with water, immersion in a 2% sodium metasilicate aqueous solution at a temperature of 85°C for 37 seconds, further immersion in water at a temperature of 90°C (pH 8.5) for 25 seconds, washing with water, drying, and aluminum Got the board.

Next, prepare a primer layer coating solution with the composition shown below. After dispersing for 1 hour using a high-pressure bulb homogenizer, it is applied to an aluminum plate a, dried for 13 minutes at 85°C, and heated at 10100O/ Full-body exposure of ci was performed. It was further dried at 100°C for 4 minutes to form a primer with a thickness of 4 μm.

(Brimer composition) 1) Diazo resin 10 parts 2) Hydroxyl group-containing polymer 90 parts 3) Zinc oxide
50 parts 4) Solvent 850 parts The synthesis of the hydroxyl group-containing polymer and diazo resin used in the primer layer is shown.

<Synthesis of hydroxyl group-containing polymer> Add 2-hydroxyethyl methacrylate (29.3) to a mixed solvent of 65 g of acetone and 65 g of methanol under a nitrogen stream.
g (0,225 mol) methyl methacrylate 27.5
g (0,275 mol) and 1.23 g of azobisisobutyronitrile were dissolved, and while stirring this mixture,
The mixture was refluxed at 60°C for 6 hours. After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound, and vacuum-dried at 50°C day and night.

Synthesis of diazo resin 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under water cooling. To this reaction solution, 1.35 g (45 mmol) of paraformaldehyde was gradually added so that the reaction temperature did not exceed 10''C.

This reaction mixture was added dropwise to ethanol at 500 mA under water cooling, and the resulting precipitate was filtered. After washing with ethanol,
This precipitate was dissolved in 100 mj2 of pure water, and 6
．． A cold concentrated aqueous solution of 8 g of zinc chloride was added. The resulting precipitate was filtered and washed with ethanol.
0mjl! It was dissolved in pure water, and to this solution was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and then dried to obtain diazo resin 1.

? [Preparation of Photosensitive Layer and Silicone Layer] A photosensitive layer having a combination of a photosensitive layer and a binder shown in Table 1 was prepared on the above-mentioned brimer in the following composition ratio, was coated with a whirler, and was dried at 85° C. for 3 minutes.

The thickness of the photosensitive layer was: )+g/dm2.

Binder: 100 parts Photosensitive layer: 50 parts 2-trichloromethyl-5-(β(2'henzofuryl)vinyl)-1
, 3,4-oxadizole...2 parts Victoria Pure Blue BOH1 part Methyl lactate...1000 parts Table 1 Combination of photosensitive layer and binder Next, 1.8 g of the following silicone rubber composition was applied on the photosensitive layer by dry weight. /n() and dried in hot air at 90°C for 10 minutes.

(Silicone rubber layer composition) Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 52.000) 100 parts Triacetoxymethylsilane 10 parts Dibutyltin laurate 0.8 parts'' Isopar E (manufactured by Esso Chemical Co., Ltd.) 900 parts Next, a single-sided matted polypropylene film having a thickness of 5 μm was laminated on the silicone rubber layer to obtain a photosensitive lithographic printing plate that did not require dampening water.

After a (Ugura Plate Console Wedge (Test Kyle)) was vacuum-adhered to the upper surface of the above plate material, it was exposed to light at 520 mJ/ctA using a metal halide lamp as a light source. Next, after soaking in the following developer at 27°C for 1 minute, standard development was performed by rubbing the surface of the plate material with a pad impregnated with the developer, and the image area was further coated with a dyeing solution of the following composition on the cloth. Dyeing was carried out by rubbing lightly on the plate and rinsing with water.

(Developer) Potassium hydroxide 1.0 parts Potassium sulfite 2.0 parts Potassium metasilicate 3.0 parts Water
91 parts (staining liquid) "Tulfit" (manufactured by Clarei Soprene Chemical ■, solvent) 91 parts "Rheodol TW-0120" (manufactured by Kao Corporation, surfactant) 0.5 parts Benzyl alcohol 5.0 parts Victoria Pure Blue BOH 1,0 Department water
After dyeing 100 copies, the good reproducibility range of halftone dots (Brunner dots) was examined to examine developability. The results are shown in the column labeled Developability in Table 2.

Further, the developer solution was diluted twice with water and the same treatment was applied to each plate, and the reproduction range of the halftone dots was investigated. The results are shown in the column labeled underprint in Table 2.

Next, each standard developed plate was installed on a Heidelberg GTO printing machine with the dampening water supply device removed, and the Toyo Ink T
Printed with OYOKING ULTRA Aquares G red ink and examined the reproduction range of halftone dots on the printed matter. The results are shown in the column labeled Printed Materials in Table 2.

To examine safelight properties, each plate was exposed to white fluorescent light (300 fx on the plate surface) for an exposure time of 10 minutes. After this, the positive film was exposed in close contact and subjected to normal development processing, and the quality of the image was checked by halftone dots.

The results are shown in the column labeled Safelight property in Table 2.

(Effects of the Invention) From the above results, it was confirmed that the photosensitive lithographic printing plate that does not require dampening water of the present invention can be developed with an alkaline aqueous solution and has excellent safelight properties.

Claims (1)

[Claims] In a dampening water-free photosensitive lithographic printing plate in which at least a primer layer, a photosensitive layer, and a silicone rubber layer are coated in this order on a base plate, the photosensitive layer comprises at least (A) 1,2-naphthoquinone-2-diazide. -4 sulfonic acid ester compound and (B) a polymer having in its molecular structure a structural unit having a phenolic hydroxyl group.